CN111853380A

CN111853380A - Hose, abrasion resistant composition and hose manufacturing process

Info

Publication number: CN111853380A
Application number: CN202010773756.5A
Authority: CN
Inventors: K·高普兰; R·J·伦哈特; 嵇根定; P·莫罗
Original assignee: Cooper Standard Automotive Inc
Current assignee: Cooper Standard Automotive Inc
Priority date: 2014-07-02
Filing date: 2015-07-01
Publication date: 2020-10-30
Also published as: CN106715989B; US10895335B2; WO2016004204A1; EP3164633B1; US20190346072A1; EP3164633A4; EP3164633A1; US20170130876A1; US10371292B2; CN106715989A

Abstract

A hose made from a composition comprising one or more of EPR, EPDM, a silane-grafted polyolefin and a silicone-modified polyolefin; and one or more of fibers, polyamide powder, and ultra-high molecular weight polyethylene powder.

Description

Hose, abrasion resistant composition and hose manufacturing process

This application is a divisional application entitled "hose, wear-resistant composition and hose manufacturing process" having application number 201580046407.0 and having application date 1/7/2015.

Background

The present disclosure relates to hose compositions, hoses useful in vehicles, and methods of forming hoses.

Composite hoses are commonly used in the automotive industry for transporting fluids in, for example, heating/cooling or conveying systems. Such tubes typically comprise a Nylon woven jacket (Nylon woven flex) or the like which is applied over all or part of the composite tube to protect the tube surface from damage due to abrasion during use. However, the addition of nylon woven sleeves or the like is expensive and time consuming due to the labor required in the assembly operation.

There is a need to develop new compositions for making hoses that have good abrasion resistance and can be produced at lower monetary and time costs.

Brief description of the drawings

The present disclosure relates to a composition comprising one or more of fibers, polyamide powder, and ultra-high molecular weight polyethylene powder; and one or more of EPR (ethylene-propylene copolymer rubber), EPDM (ethylene-propylene-diene terpolymer rubber), silicone-modified polyolefin, and silane-grafted polyolefin. The composition is useful for producing hoses, particularly for vehicles.

Disclosed embodiments are hoses having an outermost layer formed from the composition.

These and other non-limiting features of the disclosure are disclosed in more detail below.

Drawings

The following is a brief description of the drawings, which are intended to illustrate exemplary embodiments of the disclosure, and not to limit the embodiments of the disclosure.

Fig. 1 illustrates an exemplary embodiment of a hose of the present disclosure.

Fig. 2 shows cross-sectional and side views of exemplary layers of the hose of the present disclosure.

Detailed Description

The components, processes and apparatus disclosed herein can be more fully understood with reference to the accompanying drawings. These drawings are merely schematic representations based on convenience of demonstrating the present disclosure, and as such, are not intended to refer to the relative sizes and dimensions of the devices or components of the present disclosure, and/or to define or limit the scope of the exemplary embodiments.

Although the following description uses specific terms for the sake of clarity, these terms are used only to refer to particular structures of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure. In the following drawings and description, it is to be understood that like reference numerals refer to parts having like functions.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

Numerical values in the specification and claims of this application should be understood to include numerical values that are the same when reduced to the same number of significant figures and numerical values that differ from the stated value by less than the experimental error of conventional measurement techniques of the type described in this application for determining the stated value.

All ranges disclosed herein are inclusive of the recited endpoints and independently combinable (e.g., a range of "2 to 10" is inclusive of the endpoints 2 and 10 and all intermediate values). The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value; they are not sufficiently accurate to include values close to these ranges and/or values.

A value modified by a term or terms (such as "about" and "substantially") may not be limited to the precise value specified. Similar language may correspond to the precision of the instrument used for the measurement. The modifier "about" should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression "about 2 to about 4" also discloses the range "2 to 4".

The term "ultra-high molecular weight polyethylene" refers to polyethylene having exceptionally long chains and having millions of molecular weights.

The hose of the present disclosure includes a layer comprising one or more of EPR, EPDM, a silicone-modified polyolefin, and a silane-grafted polyolefin; and one or more of fibers and ultra-high molecular weight polyethylene powder for improving wear resistance. In some embodiments, the layer comprises both a silicone-modified polyolefin and a silane-grafted polyolefin. This layer is the outermost layer of the hose. In some embodiments, the silicone-modified polyolefin is a silicone-modified ethylene-propylene-diene elastomer.

The ultra-high molecular weight polyolefin has a molecular weight in the range of about 1 million g/mol to about 6 million g/mol. In some embodiments, the ultra-high molecular weight polyolefin has a molecular weight in the range of about 3.1 million g/mol to about 5.67 million g/mol. In other embodiments, the ultra-high molecular weight polyolefin has a molecular weight in a range of about 1.5 million g/mol to about 2.5 million g/mol, including about 2 million g/mol. The ultra-high molecular weight polyolefin may be prepared using any catalytic technique. In some embodiments, a ziegler catalyst is employed. The ultra-high molecular weight polyolefin has a density in the range of about 0.930g/cm³To about 0.950g/cm³Including about 0.94g/cm³。

One or more types of fibers may be included. Non-limiting examples of fibers include aramid fibers (e.g., treated chopped aramid fibers), nylon fibers, glass fibers, carbon fibers, and fibers derived from 1, 3-propanediol moieties (e.g., dupont Sorona fibers).

The hose composition further comprises one or more heat resistant polymers. Non-limiting examples of heat resistant polymers include ethylene-propylene rubber (EPM) and ethylene propylene diene rubber (EPDM).

Fig. 1 illustrates an exemplary composite hose 5 of the present disclosure. The hose comprises a conduit 1, a reinforcement layer 2, a cover layer 3 and optionally a protective layer 4. The covering layer 3 and/or the protective layer 4, when present, may comprise a composition comprising fibres, polyamide powder and/or ultra high molecular weight polyethylene powder.

The reinforcement layer 2 has yarns for achieving a good pressure resistance (e.g. resistance to 3 bar pressure at 150 ℃). The reinforcing yarn comprises a knit, a braid, or a spiral. The knitting includes lock stitching and/or flat stitching.

The fabric of the reinforcement layer 2 comprises an aramid (such as KEVLAR)^TMOr TWARON^TM) Polyamide, polyester and RAYON^TM、NOMEX^TMOr TECHNORA^TM。

In some embodiments, the yarns may be replaced with chopped fibers mixed with a silane-grafted polyolefin composition, it being understood that other suitable reinforcements may be used without departing from the scope and intent of the present disclosure.

The conduit 1 and/or the cover layer 3 may comprise a silane-grafted polyolefin. Optionally, the cover layer 3 is formed from a composition containing ultra-high molecular weight polyolefin powder, polyamide powder and/or fibers. The cover layer 3 may also comprise silicone-modified polyolefins, EPR and/or EPDM.

The cover layer 3 may have a thickness of about 0.5mm to about 6.0mm, including about 1.5mm to about 4.5mm, and including about 2mm to about 3 mm.

The protective layer 4 may be formed of a composition comprising one or more of EPR, EPDM, a silane-grafted polyolefin and a silicone-modified polyolefin; and comprises one or more of ultra-high molecular weight polyethylene powder, polyamide powder and/or fibers.

The protective layer 4 may be applied (e.g. injection moulded or extruded) to the entire layer of the cover layer 3 or at selected locations where improved wear resistance is required. The applied cover layer 4 may cover at least or up to 5% of the surface area of the cover layer 3, including at least or up to 10%, at least or up to 15%, at least or up to 20%, at least or up to 25%, at least or up to 30%, at least or up to 35%, at least or up to 40%, at least or up to 45%, at least or up to 50%, at least or up to 55%, at least or up to 60%, at least or up to 70%, at least or up to 75%, at least or up to 80%, at least or up to 85%, at least or up to 90%, and at least or up to 95%.

The protective layer 4 may have a thickness of about 0.2mm to about 2.0mm, including about 0.6mm to about 1.6mm, and including about 1.0mm to about 1.2 mm.

The composition of the covering layer 3 and/or the protective layer 4 may contain (a) from about 5 to about 95phr of EPR, EPDM, silicone-modified polyolefin and/or silane-grafted polyolefin, and (B) from about 5 to about 60phr of ultrahigh molecular weight powder, polyamide powder and/or fibers. In some embodiments, component (a) is included in an amount of about 30 to about 70phr and component (B) is included in an amount of about 20 to about 45 phr. In particular embodiments, the compositions contain about 50phr of component (a) and about 30phr of component (B).

In some embodiments, the hose 5 is comprised of the conduit 1, the reinforcement layer 2, the cover layer 3, and the protective layer 4. In other embodiments, the hose 5 is composed of the conduit 1, the reinforcement layer 2 and the cover layer 3. In a further embodiment, the reinforcement layer 2 may be omitted.

Optionally, layer 3 and/or layer 4 are steam cured.

The particle size of the polyamide and/or ultra-high molecular weight powder can range from about 10 μm to about 100 μm, including from about 20 μm to about 80 μm, from about 25 μm to about 65 μm, and about 30 μm. In some embodiments, at least 65% of the particles have a particle size in the range of about 20 to about 40 μm.

The silane-grafted polyolefin may crosslink upon exposure to moisture and/or heat to form an elastomeric material. Crosslinked polyolefins can be used instead of the existing EPDM rubber formulations to make automotive hoses.

Advantageously, the composition used to form the cover layer 3 and/or the protective layer 4 requires only a limited number of ingredients (e.g., 10, 9, 8, 7, 6, 5, 4, or 3 ingredients). These ingredients can be combined in an extruder during extrusion (e.g., a single-step Monosil process or a two-step Sioplas process) so that no additional step of mixing and transporting the rubber compound is required prior to extrusion.

The specific gravity of the silane-grafted polyolefin and the crosslinked polyolefin of the present disclosure may be lower than that of existing EPDM formulations. The reduced specific gravity of the material produces lower weight parts, thereby helping automobile manufacturers to meet the ever-increasing demand for improved fuel economy. For example, a representative material of the present disclosure may have a specific gravity of about 0.86g/cm³To about 0.96g/cm³(which is significantly less than 1.10 to 1.40 g/cm)³Comparable conventional specific gravity).

The compositions of the present disclosure also reduce the carbon footprint of extrusion equipment used to make hoses or other articles because significant amounts of natural gas and/or electric furnaces are not required for vulcanization. In contrast, silane grafted polyolefins can be cured using a more efficient low pressure steam chamber while producing minimal smoke.

The composition is the same or similar to the composition disclosed in co-owned provisional patent application No. 61/835,157 filed on 6/14/2013.

The polyolefin elastomer may be a block copolymer, an ethylene/alpha-olefin copolymer, a propylene/alpha-olefin copolymer, an EPDM, or a mixture of two or more of these materials. Exemplary block copolymers include INFUSE^TMThose sold (e.g., INFUSE)^TM9000). Exemplary ethylene/alpha-olefin copolymers include those known under the trade name VISTA AXX^TM(e.g., VISTA MAX 6102), TAFMER^TM(e.g., TAFMER DF710) and ENGAGE^TM(e.g., ENGAGE 8150). Exemplary propylene/α -olefin copolymers include those sold under the trade name TAFMER^TMThose sold by XM level. The EPDM has a diene content of about 0.5 to about 10 wt%.

In some embodiments, the olefin is selected from: homopolymers or blends of homopolymers of olefins, copolymers or blends of copolymers of two or more olefins, and blends of homopolymers and copolymers.

The olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-propene, 1-hexene and 1-octene. The olefins may be prepared by employing any process and optionally any catalyst suitable for polymerizing ethylene and alpha-olefins. Metallocene catalysts can be used to prepare low density ethylene/alpha-olefin polymers.

Suitable polyethylenes include, but are not limited to, polyethylenes prepared by homopolymerization of ethylene or copolymerization of ethylene and a higher 1-olefin comonomer.

Suitable polypropylenes include, but are not limited to, polypropylenes produced by the homopolymerization of propylene or the copolymerization of propylene and an olefin comonomer.

The term "comonomer" refers to an olefin comonomer suitable for polymerization with an olefin monomer, such as ethylene or propylene monomer. Comonomers include, but are not limited to, aliphatic C₂-C₂₀An alpha-olefin. Suitable aliphatic C₂-C₂₀Examples of the α -olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. In one embodiment, the comonomer is vinyl acetate. The term "copolymer" refers to a polymer prepared by linking two different types of polymers in the same polymer chain. The term "homopolymer" refers to a polymer prepared by linking olefin monomers in the absence of a comonomer. In some embodiments, the amount of comonomer can be from about 0 to about 12 weight percent, including from about 0 to about 9 weight percent and greater than 0 to about 7 weight percent, based on the weight of the polyolefin. In some embodiments, the comonomer content is greater than about 2 mole percent of the final polymer, including greater than about 3 mole percent and greater than about 6 mole percent. The copolymers may be random or block (heterophasic) copolymers. In some embodiments, the polyolefin is a random copolymer of propylene and ethylene.

The polyethylenes used in the present disclosure can be classified into several types, including but not limited to LDPE (low density polyethylene), LLDPE (linear low density polyethylene), and HDPE (high density polyethylene). In another category, polyethylene can be classified as Ultra High Molecular Weight (UHMW), High Molecular Weight (HMW), Medium Molecular Weight (MMW), and Low Molecular Weight (LMW). The polyethylene may be of ultra low densityAn ethylene elastomer. The ultra-low density ethylene elastomer may have a density of 0.85g/cm³Or larger.

The polyolefin may comprise an LDPE/silane copolymer or blend.

The polyolefin (e.g., polyethylene) may be prepared using any catalyst known in the art, including but not limited to a chromium catalyst, a ziegler-natta catalyst, a metallocene catalyst, or a post-metallocene catalyst.

In some embodiments, the polyolefin has a molecular weight distribution M_w/M_nLess than or equal to about 5, including less than or equal to about 4, about 1 to about 3.5, and about 1 to about 3.

The polyolefin has a melt viscosity in the range of about 2,000cP to about 50,000cP as measured using a brookfield viscometer at a temperature of about 177 ℃. In some embodiments, the melt viscosity is from about 4,000cP to about 40,000cP, including from about 5,000cP to about 30,000cP and from about 6,000cP to about 18,000 cP.

The polyolefin has a melt index (T2) of from about 20.0g/10min to about 3,500g/10min, including from about 250g/10min to about 1,900g/10min and from about 300g/10min to about 1,500g/10min, measured at 190 ℃ under a 2.16kg load. In some embodiments, the polyolefin has a fractional melt index of 0.5g/10min to about 3,500g/10 min.

The polyolefin may be polymerized in two reactors, wherein the first polymer is polymerized in the first reactor and the second polymer is polymerized in the second reactor. The second polymer may have a higher molecular weight, a different density, and/or be heterogeneous. The reactors may be connected in series or in parallel.

In some embodiments, a blend of two or more polyolefins is silanized and/or cured. The blend may include an ethylene/alpha-olefin polymer and a propylene/alpha-olefin polymer.

The polymers and resins of the present disclosure may be treated with one or more stabilizers (e.g., antioxidants). The polymer may be treated before grafting/modifying, after grafting/modifying, before crosslinking and/or after crosslinking. Other additives may also be included. Non-limiting examples of additives include antistatic agents, dyes, pigments, UV light absorbers, nucleating agents, fillers, slip agents, plasticizers, flame retardants, lubricants, processing aids, smoke suppressants, antiblocking agents, and viscosity control agents. The antioxidant may be present in an amount of less than 0.5% by weight of the composition, including less than 0.2% by weight.

In some embodiments, the polyolefin elastomer has a density of less than 1.0g/cm³Including less than about 0.92g/cm³. The density may be about 0.85g/cm³To about 0.96g/cm³。

The polyolefin elastomer may be present in an amount of greater than 0% to about 100% by weight of the composition. In some embodiments, the amount of polyolefin elastomer is from about 30 wt% to about 70 wt%.

The polyolefin elastomer may have a percent crystallinity of less than about 40%, less than about 35%, less than about 30%, less than about 25%, or less than about 20%. In some embodiments, the crystallinity ranges from about 2% to about 60%.

The silane grafted to the polyolefin may be selected from alkoxysilanes, silazanes and siloxanes.

Non-limiting examples of silazanes include hexamethyldisilazane (HMDS or bis (trimethylsilyl) amine). Non-limiting examples of siloxane compounds include Polydimethylsiloxane (PDMS) and octamethylcyclotetrasiloxane.

In some embodiments, the silane is an alkoxysilane. As used herein, the term "alkoxysilane" refers to a compound comprising a silicon atom, at least one alkoxy group, and at least one other organic group, wherein the silicon atom is bonded to the organic group by a covalent bond. Preferably, the alkoxysilane is selected from alkylsilanes; an acryl silane; a vinyl silane; an aromatic silane; an epoxy silane; aminosilane and compound having-NH₂、-NHCH₃or-N (CH)₃)₂An amine of (a); ureido silane; a mercaptosilane; and alkoxysilanes having a hydroxyl group (i.e., -OH). The acryl silane may be selected from the group including: beta-acryloxyethyltrimethoxysilane; beta-acryloxypropyltrimethoxysilane; gamma-acryloxyethyltrimethoxysilane; gamma-acryloylOxypropyltrimethoxysilane; beta-acryloxyethyltriethoxysilane; beta-acryloxypropyltriethoxysilane; gamma-acryloxyethyltriethoxysilane; gamma-acryloxypropyltriethoxysilane; beta-methacryloyloxyethyltrimethoxysilane; beta-methacryloxypropyltrimethoxysilane; gamma-methacryloyloxyethyltrimethoxysilane; gamma-methacryloxypropyltrimethoxysilane; beta-methacryloyloxyethyltriethoxysilane; beta-methacryloxypropyltriethoxysilane; gamma-methacryloyloxyethyltriethoxysilane; gamma-methacryloxypropyltriethoxysilane; 3-methacryloxypropylmethyldiethoxysilane. The vinyl silane may be selected from the group comprising: vinyl trimethoxysilane; vinyltriethoxysilane; p-styryl trimethoxysilane; methyl vinyl dimethoxy silane; vinyl dimethyl methoxysilane; divinyldimethoxysilane; vinyltris (2-methoxyethoxy) silane and vinylbenzylethylenediamine-propyltrimethoxysilane. The aromatic silane may be selected from phenyltrimethoxysilane and phenyltriethoxysilane. The epoxy silane may be selected from the group comprising: 3-glycidoxypropyltrimethoxysilane; 3-glycidoxypropylmethyldiethoxysilane; 3-glycidoxypropyltriethoxysilane; 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and glycidoxypropylmethyldimethoxysilane. The aminosilane may be selected from the group comprising: 3-aminopropyltriethoxysilane; 3-aminopropyltrimethoxysilane; 3-aminopropyldimethylethoxysilane; 3-aminopropylmethyldiethoxysilane; 4-aminobutyltriethoxysilane; 3-aminopropyl diisopropylethoxysilane; 1-amino-2- (dimethylethoxysilyl) propane; (aminoethylamino) -3-isobutyldimethylmethoxysilane; n- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane; (aminoethylaminomethyl) phenethyltrimethoxysilane; n- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; n- (2-aminoethyl) -3-aminopropyltrimethoxysilane; n- (2-aminoethyl) -3-aminopropyltriethoxySilane; n- (6-aminohexyl) aminomethyltrimethoxysilane; n- (6-aminohexyl) aminomethyltrimethoxysilane; n- (6-aminohexyl) aminopropyltrimethoxysilane; n- (2-aminoethyl) -1, 1-aminoundecyltrimethoxysilane; 1, 1-aminoundecyltriethoxysilane; 3- (m-aminophenoxy) propyltrimethoxysilane; m-aminophenyl trimethoxysilane; p-aminophenyl trimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; n-methylaminopropylmethyldimethoxysilane; n-methylaminopropyltrimethoxysilane; (ii) dimethylaminoethoxyethylsilane; (N, N-dimethylaminopropyl) trimethoxysilane; (N-acetylcyano) -3-aminopropyltrimethoxysilane; n-phenyl-3-aminopropyltrimethoxysilane; n-phenyl-3-aminopropyltriethoxysilane; phenylaminopropyl trimethoxysilane; aminoethylaminopropyltrimethoxysilane and aminoethylaminopropylmethyldimethoxysilane. The ureido silane may be 3-ureidopropyltriethoxysilane. The mercaptosilane may be selected from the group comprising: the alkoxysilane having a hydroxyl group of 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane may be selected from the group consisting of: hydroxymethyl triethoxysilane; n- (hydroxyethyl) -N-methylaminopropyltrimethoxysilane; bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; n- (3-triethoxysilylpropyl) -4-hydroxybutyramide; 1,1- (triethoxysilyl) undecanol; triethoxysilylundecanol; an acetal of ethylene glycol; and N- (3-ethoxysilylpropyl) glucamide.

The alkylsilane may be represented by the general formula: r_nSi(OR’)_4-nWherein: n is 1, 2 or 3; r is C_1-20An alkyl group; and R' is C_1-20An alkyl group.

The term "alkyl" by itself or as part of another substituent refers to a straight or branched chain or cyclic saturated hydrocarbon group connected by a single carbon-carbon bond having from 1 to 20 carbon atoms (e.g., from 1 to 10, such as from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms). When a subscript is used herein after a carbon atom, the subscript isRefers to the number of carbon atoms that the group contains. Thus, for example, C_1-6Alkyl refers to alkyl groups containing 1 to 6 carbon atoms. Examples of alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, f-butyl, 2-methylbutyl, pentyl, isopentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, decyl and its isomers, dodecyl and its isomers.

The term "C_2-20Alkenyl "by itself or as part of another substituent means an unsaturated hydrocarbon group, which may be straight or branched, containing one or more carbon-carbon double bonds having from 2 to 20 carbon atoms. C_2-6Examples of alkenyl groups are vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2, 4-pentadienyl and the like.

The alkylsilane may be selected from the group comprising: methyltrimethoxysilane; methyltriethoxysilane; ethyltrimethoxysilane; ethyltriethoxysilane; propyl trimethoxy silane; propyltriethoxysilane; hexyltrimethoxysilane; hexyltriethoxysilane; octyl trimethoxysilane; octyl triethoxysilane; decyl trimethoxy silane; decyl triethoxysilane; dodecyl triethoxy silane; tridecyltrimethoxysilane; dodecyl triethoxy silane; hexadecyl trimethoxy silane; hexadecyl triethoxy silane; octadecyltrimethoxysilane; octadecyltriethoxysilane, trimethylmethoxysilane, methylhydroxydimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isobutyltrimethoxysilane, n-butyltrimethoxysilane, n-butylmethyldimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, triphenylsilanol, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, dicyclopentyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, dicyclohexyldimethoxysilane.

The silane compound may be selected from triethoxyoctylsilane, trimethoxyoctylsilane, and combinations thereof.

Examples of silanes include, but are not limited to, those of the formula CH₂＝CR-(COO)_x(C_nH_2n)_ySiR’₃Wherein R is a hydrogen atom or a methyl group; x is 0 or 1; y is 0 or 1; n is an integer from 1 to 12; each R' may be an organic group and may be independently selected from alkoxy (e.g. methoxy, ethoxy, butoxy) groups having 1 to 12 carbon atoms, aryloxy (e.g. phenoxy), aralkyloxy (e.g. benzyloxy), aliphatic acyloxy (e.g. formyloxy, acetoxy, propionyloxy) groups having 1 to 12 carbon atoms, amino or substituted amino (e.g. alkylamino, arylamino) or lower alkyl groups having 1 to 6 carbon atoms. Both x and y may equal 1. In some embodiments, no more than one of the three R' groups is alkyl. In other embodiments, no more than two of the three R' groups are alkyl groups.

Any silane or mixture of silanes that can effectively graft and crosslink olefin polymers can be used in the practice of the present invention. Suitable silanes include, but are not limited to, unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group (e.g., vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or gamma- (meth) acryloxyallyl) and a hydrolyzable group (e.g., hydrocarbyloxy (hydrocarbyloxy) or hydrocarbylamino). Non-limiting examples of hydrolyzable groups include, but are not limited to, methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino groups. In some embodiments, the silane is an unsaturated alkoxysilane that can be grafted onto the polymer. Other exemplary silanes include vinyltrimethoxysilane, vinyltriethoxysilane, 3- (trimethoxysilyl) propyl methacrylate gamma- (meth) acryloxypropyltrimethoxysilane), and mixtures thereof.

The silane content of the silane-grafted polyolefin may be greater than 0 to about 10 weight percent, including about 0.5 to about 5 weight percent. The amount of silane can vary based on the nature of the olefin polymer, the silane, processing conditions, grafting efficiency, application, and other factors. The amount of silane may be at least 2 wt%, including at least 4 wt% or at least 5 wt%, based on the weight of the reactive composition. In other embodiments, the amount of silane may be at least 10 wt% based on the weight of the reactive composition.

Optionally, crosslinking is initiated by catalyst or electron beam radiation. Non-limiting examples of catalysts include organic bases, carboxylic acids, and organometallic compounds (e.g., organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc, and tin). The catalyst may be selected from fatty acids and metal complex compounds, such as metal carboxylates; aluminum triacetylacetonate, iron triacetylacetonate, manganese tetraacetylacetonate, nickel tetraacetylacetonate, chromium hexa-acetylacetonate, titanium tetraacetylacetonate and cobalt tetraacetylacetonate; metal alkoxides such as aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide, titanium propoxide, and titanium butoxide; metal salt compounds such as sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate and dibutyltin di (2-ethylhexanoate); acidic compounds such as formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid esters of hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid and dialkyl phosphorous acid; acids such as p-toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, itaconic acid, oxalic acid and maleic acid, ammonium salts, lower amine salts 35 or polyvalent metal salts of these acids, sodium hydroxide, lithium chloride; organometallic compounds such as diethyl zinc and titanium tetra (n-butoxide); and amines such as dicyclohexylamine, triethylamine, N-dimethylbenzylamine, N' -tetramethyl-1, 3-butanediamine, diethanolamine, triethanolamine and cyclohexylethylamine. In some embodiments, the catalyst is selected from the group consisting of dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, and cobalt naphthenate. A single catalyst or a mixture of catalysts may be used. In some embodiments, the catalyst may be present in an amount of about 0.01 wt% to about 1.0 wt%.

In some embodiments, the crosslinking system uses a combination of radiation, heat, moisture, and/or a crosslinking agent.

Optionally, a grafting initiator is used in the grafting process. The grafting initiator may be selected from halogen molecules, azo compounds (e.g. azobisisobutyl), carboxylic peroxyacids, peroxyesters, peroxyketals and peroxides (e.g. alkyl hydroperoxides, dialkyl peroxides and diacyl peroxides). In some embodiments, the grafting initiator is an organic peroxide selected from the group consisting of di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 1, 3-bis (t-butylperoxyisopropyl) benzene, n-butyl-4, 4-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butyl peroxybenzoate, and bis (2-methylbenzoyl) peroxide, bis (4-methylbenzoyl) peroxide, t-butyl peroctoate, cumene hydroperoxide, methylethylketone peroxide, lauryl peroxide, t-butyl peracetate, di-t-amyl peroxide, t-amyl peroxybenzoate, tert-amyl peroxybenzoate, di-t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylyelohexane, α '-bis (t-butylperoxy) -1, 3-diisopropylbenzene, α' -bis (t-butylperoxy) -1, 4-diisopropylbenzene, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane and 2, 5-bis (t-butylperoxy) -2, 5-dimethyl-3-hexyne and 2, 4-dichlorobenzoyl peroxide. Exemplary peroxides include those under the trade name LUPEROX^TM(e.g., LUPEROX)^TM101) Those sold.

In some embodiments, the grafting initiator is present in an amount of greater than 0 to about 2 weight percent of the composition, including about 0.15 to about 1.2 weight percent of the composition. The amount of initiator and silane used will affect the structure of the final silane-grafted polymer (e.g., the degree of grafting in the grafted polymer and the degree of crosslinking in the cured polymer). In some embodiments, the reactive composition contains at least 100ppm of initiator or at least 300ppm of initiator. The initiator may be present in an amount of 300ppm to 1500ppm or 2000 ppm. Silane: the initiator weight ratio may be from about 20:1 to 400:1, including from about 30:1 to about 400:1 and from about 48:1 to about 350:1, and from about 55:1 to about 333: 1.

The grafting reaction can be conducted under conditions that optimize grafting to the interpolymer backbone while minimizing side reactions, such as homopolymerization of the grafting agent. The grafting reaction can be carried out in the melt, in solution, in the solid state and/or in the swollen state. Silanization can be carried out in a wide variety of equipment, for example, twin screw extruders, single screw extruders, Brabender, internal mixers (e.g., Banbury mixers), and batch reactors. In some embodiments, the polyolefin, silane, and initiator are mixed in the first section of the extruder. The melting temperature may be from about 120 ℃ to about 260 ℃, including from about 130 ℃ to about 250 ℃.

The composition optionally includes one or more fillers. The filler may be extruded with EPR, EPDM, silane-grafted polyolefin and/or silicone-modified polyolefin. The filler may be selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, clays, talc, carbon black and silica. These materials may be pyrolyzed or calcined.

The metal of the metal oxide, metal hydroxide, metal carbonate, metal sulfate, or metal silicate may be selected from alkali metals (e.g., lithium, sodium, potassium, rubidium, cesium, and francium); alkaline earth metals (e.g., beryllium, magnesium, calcium, strontium, barium, and radium); transition metals (e.g., zinc, molybdenum, cadmium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, technetium, neodymium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, indium, platinum, gold, mercury, , chromium, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, technetium, neodymium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, indium, platinum, gold, mercury, ,

And cn (copernium)); late transition metals (e.g., aluminum, gallium, indium, tin, thallium, lead, bismuth, and polonium); lanthanides (e.g., lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, andlutetium); actinides (e.g., actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium); germanium, arsenic, antimony; and an astatine.

Fillers may be present in amounts of greater than 0 to about 50 weight percent, including about 1 to about 20 weight percent and about 3 to about 10 weight percent.

One-stage silane crosslinking involves extruding a direct mixture of a polymer resin and a silane concentrate containing a catalyst. The extrudate may then be crosslinked in the presence of moisture/heat. In two-stage crosslinking, the silane is first grafted onto the polymer molecular chains according to known reactions, resulting in a silane-grafted copolymer.

Subsequently, the silane-grafted copolymer is mixed with a silanol condensation catalyst and then exposed to moisture and/or heat to effect crosslinking of the copolymer in a two-step reaction. Alternatively, the composition may be crosslinked by "Ambicat", where ambient moisture is sufficient to effect crosslinking over a longer period of time (e.g., about 48 hours). First, water hydrolyzes the silane to produce silanol. The silanols then condense to form intermolecular, irreversible Si-O-Si crosslinking sites.

The content of crosslinked silane groups and thus the final polymer properties can be adjusted by controlling the production process, including the amount of catalyst used. The amount of crosslinking can be determined using the gel test (ASTM D2765).

Curing may occur over a period of time of greater than 0 to about 20 hours. In some embodiments, curing occurs over a period of about 1 to about 8 hours, including about 3 to about 6 hours.

The temperature during curing may be from about 50 to about 150 ℃, including from about 80 to about 100 ℃ and from about 85 to about 95 ℃.

The humidity during curing may be from about 30 to about 100%, including from about 40 to about 100% and from about 50 to about 100%.

The number average molecular weight of the graft polymer ranges from about 4,000g/mol to about 30,000g/mol, including from about 5,000g/mol to about 25,000g/mol and from about 6,000g/mol to about 14,000 g/mol. The graft polymer may have a weight average molecular weight of from about 8,000g/mol to about 60,000g/mol, including from about 10,000g/mol to about 30,000 g/mol.

Optionally, the composition and/or article formed therefrom further comprises one or more TPVs and/or EPDM with or without silane grafted moieties. In some embodiments, the compositions and/or articles further include other homopolymers, copolymers, and/or terpolymers of ethylene (e.g., LDPE, graft polymers, maleated polymers, EVA copolymers, ethylene n-butyl acrylate copolymers, and vinyl methacrylate copolymers); homopolymers, copolymers and/or terpolymers of propylene; rubber block copolymers (e.g., copolymers having an A-B-A configuration, an A-B-A-B-A-B configuration, an A-B configuration, and a star block copolymer) and other olefin-based polymers. In some embodiments, the additional polymer is present in an amount up to 50% by weight of the composition.

The compositions and/or articles may also include waxes (e.g., paraffin waxes, microcrystalline waxes, HDPE waxes, LDPE waxes, thermally degraded waxes, by-product polyethylene waxes, optionally oxidized fischer-tropsch waxes, and functionalized waxes).

Tackifying resins (e.g., aliphatic hydrocarbons, aromatic hydrocarbons, modified hydrocarbons, terpenes, modified terpenes, hydrogenated terpenes, rosins, rosin derivatives, hydrogenated rosins, and mixtures thereof) may also be included. The tackifying resin may have a ring and ball softening point in the range of 70 ℃ to about 150 ℃ and a viscosity of less than about 3,000cP at 177 ℃.

The composition may include one or more oils. Non-limiting types of oils include mineral oils (e.g., white mineral oils) and naphthenic oils.

The composition may be extruded into pellets, pillows, or any other structure prior to forming into a final article.

In an embodiment, a method for making a hose comprising a silane-grafted polyolefin is disclosed.

The silane-grafted composition may be extruded with a thermoplastic extruder at a temperature of about 140 ℃ to about 220 ℃. The extruded article may be water cooled, fabric reinforced, heated to a temperature of about 100 ℃ to about 150 ℃, co-extruded from the silane-grafted composition, cooled, cut and shaped.

In some embodiments, the wall thickness of the hose is from about 1 to about 4mm, preferably from about 1.5 to about 2.5 mm.

In some embodiments, the hose is formed on or external to the mandrel in hot water or steam.

In some embodiments, the hose is formed by blow molding in a mold.

In some embodiments, reticulation of the silane grafted composition is accomplished at room temperature and under moisture (e.g., one to several days), for example, in hot water at a temperature of 20 to 90 ℃ for one to several hours, in steam at a pressure of 1 to 5 bar for 1 to 4 hours.

In some embodiments, the hose is equipped with a quick connector rather than a clamp.

The compositions of the present disclosure may be sulfur-curable or peroxide-curable.

This written description uses examples to describe the disclosure, including the best mode, and also to enable any person skilled in the art to make and use the disclosure. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. The above examples are merely illustrative of various aspects of the present disclosure, wherein equivalent alterations and/or modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In particular and unless otherwise indicated, with respect to the various functions performed by the above described components (assemblies, devices, systems, etc.), the terms (including a reference to a "means") used to describe such components are intended to correspond, even though not structurally equivalent to the disclosed structure which performs the specified function of the described component (i.e., that is functionally equivalent). In addition, while a particular feature of the disclosure may have been shown and/or described with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application. Furthermore, the terms "comprising," including, "" having, "" with, "or variants thereof, as used in the detailed description and/or claims, are intended to be inclusive in a manner similar to the term" comprising. Furthermore, this disclosure is intended to protect the combinations of elements and/or steps initially described for examination and claims, while implicitly protecting other combinations of elements and/or steps and claims during the prosecution.

Claims

1. A hose comprising an outermost layer formed from a composition comprising:

(A) at least one of a silane-grafted polyolefin, a silicone-modified polyolefin, or a combination thereof; and

(B) at least one of ultra-high molecular weight polyethylene powder, polyamide powder, and fiber.

2. The hose of claim 1, further comprising a conduit and a reinforcing layer circumferentially surrounding the conduit; wherein the outermost layer is a cover layer circumferentially surrounding the reinforcing layer.

3. The hose of claim 2, wherein the hose is comprised of a tube, a reinforcing layer, and a cover.

4. The hose of claim 1, further comprising a conduit, a reinforcing layer circumferentially surrounding the conduit, and a cover layer circumferentially surrounding the reinforcing layer; wherein the outermost layer is a protective layer circumferentially surrounding the cover layer.

5. The hose of claim 4, wherein the hose is comprised of a tube, a reinforcing layer, a cover layer, and a protective layer.

6. The hose of claim 4, wherein the protective layer circumferentially surrounds at least a portion of the cover layer, or circumferentially surrounds the entire cover layer.

7. The hose according to claim 1, wherein component (a) has an average particle size in the range of 10 μm to 100 μm.

8. The hose of claim 1 further comprising a fabric reinforcement layer.

9. The hose of claim 1, further comprising a rigid member in contact with the outermost layer.

10. The hose of claim 1, wherein the fibers are selected from aramid fibers, nylon fibers, glass fibers, and carbon fibers.

11. A hose comprising an outermost layer formed from a composition comprising:

(A) at least one of EPR, EPDM, silane-grafted polyolefin and silicone-modified polyolefin; and

(B) ultra high molecular weight polyethylene powder.

12. The hose of claim 11, further comprising a conduit and a reinforcing layer circumferentially surrounding the conduit; wherein the outermost layer is a cover layer circumferentially surrounding the reinforcing layer.

13. The hose of claim 12, wherein the hose is comprised of a tube, a reinforcing layer, and a cover.

14. The hose of claim 11, further comprising a conduit, a reinforcing layer circumferentially surrounding the conduit, and a cover layer circumferentially surrounding the reinforcing layer; wherein the outermost layer is a protective layer circumferentially surrounding the cover layer.

15. The hose of claim 14, wherein the hose is comprised of a tube, a reinforcing layer, a cover layer, and a protective layer.

16. The hose of claim 14, wherein the protective layer circumferentially surrounds at least a portion of the cover layer, or circumferentially surrounds the entire cover layer.

17. The hose of claim 11, wherein component (a) has an average particle size in the range of 10 μ ι η to 100 μ ι η.

18. The hose of claim 11 further comprising a fabric reinforcement layer.

19. The hose of claim 11, further comprising a rigid member in contact with the outermost layer.

20. An automotive heating and cooling system or an automotive transmission system comprising:

a hose; and

a rigid member in contact with the hose;

wherein the hose comprises an outermost layer in contact with the rigid member; and is

Wherein the outermost layer is formed from a composition comprising

(A) At least one of a silane-grafted polyolefin and a silicone-modified polyolefin; and

(B) at least one of treated chopped aramid fibers, polyamide powder, and ultra-high molecular weight polyethylene powder;

or wherein the outermost layer is formed from a composition comprising

(B) At least one of EPR, EPDM, a silane-grafted ethylene-propylene-diene terpolymer polyolefin or a silicone-modified ethylene-propylene-diene terpolymer polyolefin; and

(C) ultra high molecular weight polyethylene powder.